Materials and Design 33 (2012) 273283

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Materials and Design

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Effect of stabilizer on the mechanical, morphological and thermal properties of compatibilized high density polyethylene/ethylene vinyl acetate copolymer/organoclay nanocomposites
Shahin Akhlaghi a, Alireza Sharif a,b,, Mohammadreza Kalaee a, Alireza Elahi a, Mohammadhadi Pirzadeh a, Saeedeh Mazinani c, Mehdi Afshari d
a

Department of Polymer Engineering, Islamic Azad University, Tehran South Branch, Tehran, Iran Department of Polymer Science and Technology, Research Institute of Petroleum Industry (RIPI), Tehran, Iran c Amirkabir Nanotechnology Research Institute (ANTRI), Amirkabir University of Technology, Tehran, Iran d Fiber and Polymer Science, College of Textiles, North Carolina State University, Raleigh, NC, USA
b

a r t i c l e

i n f o

a b s t r a c t
In this work, the effects of a phosphate containing stabilizer on the mechanical, morphological and thermal properties of a compatibilized high density polyethylene (HDPE)/ethylene vinyl acetate (EVA) blend containing an ammonium quaternary salts modied montmorillonite were studied from both statistical and experimental aspects. According to the results obtained from simultaneous implementation of analysis of variance (ANOVA) and mean effect assessment, the formulations designed based on the optimized coupling of stabilizer into organoclay/compatibilizer system exhibited the highest tensile properties among the prepared samples. From experimental point of view, the d-spacing measurements and microscopy observations through X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively, revealed that the stabilizer not only favored the penetration of the polymeric chains between the silicate layers but also contributed to provide ner dispersion of the minor phase in the matrix. Thermal characterizations using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) showed that the stabilizer could play a role in prevention of the organic modier of the nanoclay to undergo thermo-oxidative degradation by hindering the SN2 nucleophilic substitution reactions between alkyl ammonium chains and oxygen molecules. This, we believe, is responsible for the properties enhancement, since the protective role of stabilizer might inhibit the formation of destructive degradation products which could collapse the organoclay tactoids and also deactivate the anhydride groups of the compatibilizer. 2011 Elsevier Ltd. All rights reserved.

Article history: Received 28 May 2011 Accepted 12 July 2011 Available online 23 July 2011 Keywords: A. Nanomaterials E. Mechanical H. Selection for material properties

1. Introduction Polyethylene (PE) is the most widely used polyolen polymer which accounts for 20% of the plastic production in the world [1]. PE has several practical properties such as low cost, excellent electrical insulation, good processability and resistance to chemicals [1,2]. However, there are some drawbacks with PE including low environmental stress cracking resistance (ESCR) and poor compatibility with various additives which have restricted its use in certain purposes [3,4]. Therefore, many attempts have been directed towards blending PE with other polymers to overcome these limitations. Among the existing commercial polymers, poly(ethylene-co-vinyl acetate) (EVA) is a suitable candidate for
Corresponding author at: Department of Polymer Science and Technology, Research Institute of Petroleum Industry (RIPI), Tehran, Iran. Tel./fax: +98 21 48253089. E-mail addresses: sharifa@ripi.ir, sharif.a1355@gmail.com (A. Sharif).
0261-3069/$ - see front matter 2011 Elsevier Ltd. All rights reserved. doi:10.1016/j.matdes.2011.07.044

blending with PE to improve its exibility, toughness, ESCR and transparency [5,6]. In addition, due to the presence of polar ester groups in the EVA chemical structure, it can provide higher ller loading capacity for PE [6]. There is a great body of publications dealing with the various characteristics of PE/EVA blends. For example, Khonakdar et al. [7] studied the morphological behavior of low density polyethylene (LDPE)/EVA as well as high density PE (HDPE)/EVA blends. A twophase morphology was observed for both systems and the EVA domains were smaller in the LDPE/EVA blend than those in the HDPE/EVA. Furthermore, the mechanical properties of LDPE/EVA blends have been intensively investigated by Takidis et al. [8]. They found that the tensile strength (TS) and elongation at break (EB) of the prepared blends lay between the corresponding values of the parent polymers. In addition, from the rheological point of view, Faker et al. [9] reported that in the PE/EVA blends, the interfacial interactions enhanced with increasing PE content which, in turn, led to ner and well-distributed morphology in PE-rich blends.

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Recently, the application of nanoparticles has provided researchers an excellent approach to meet the requirements of todays challenging PE/EVA blends issues. Accordingly, several investigations have been devoted to the PE/EVA based nanocomposites. For example, Hui et al. [10] studied the mechanical properties of LDPE/EVA nanocomposites lled with silica nanoparticles and showed that high and low strain moduli as well as TS of the prepared nanocomposites were improved over the neat system. Moreover, in another attempt [11], they found that oxidative degradation of a LDPE/EVA system was shifted toward higher temperatures by addition of nanosilica. Zanetti et al. [12] studied the combustion behavior of PE/EVA nanocomposites lled with organoclay. The results revealed that the heat release and the mass loss rates (MLR) were reduced by 7080% in the nanocomposites with low organoclay (25 wt%) loadings over the neat matrix. In this context, Zhang et al. [13] reported that the reduction of MLR could be signicantly improved by the synergistic effect of the organoclay and magnesium or aluminum hydroxides as ame retardants, in the LDPE/EVA based nanocomposites. In addition, the gas barrier properties of HDPE/EVA/organoclay ternary nanocomposites were highlighted by Dadfar et al. [14]. As the authors demonstrated, presence of silicate layers of the organoclay in the prepared nanocomposites introduced a tortuous path for diffusing molecules leading to reduction of gas permeability. More recently, Riahinezhad et al. [15] investigated the morphology of nanocomposite foams based on LDPE/EVA/organoclay. They found that organoclay nanoparticles acted as a nucleating agent and consequently reduced the foam cell sizes. Furthermore, Behradfar et al. [5] studied the mechanical properties of a LDPE/EVA/organoclay system. Although, TS and elastic modulus (EM) of the neat system were found to decrease by increasing the EVA content, they increased upon the rise of the EVA loading in the nanocomposites. Employing the design of experiment (DOE) methods seems a vital and reasonable way for studying the effect of changing a wide range of parameters, simultaneously. Nevertheless, regarding the published reports on the PE/EVA/organoclay systems, one could acknowledge that the investigations concerning the application of experimental design for comparative analysis of the effect of various additives on the mechanical properties of such nanocomposites are lacking in the open literature. In addition, despite the promising potential of PE/EVA/organoclay nanocomposites for utilizing in different industrial applications, no attempts were made on optimizing the mechanical properties of these systems. Our aim in this research was therefore to explore concentrations of the organoclay, compatibilizer and stabilizer, three components used usually to prepare various polymeric nanocomposites, which lead one to a PE/EVA/organoclay system with optimized mechanical properties. To this end, the inuence of the above mentioned additives on the mechanical properties of the PE/EVA/ organoclay nanocomposites were statistically investigated using the Taguchi experimental design approach. Furthermore, the effects of the additives on the nanocomposites morphology and thermal behaviors were also studied by X-ray diffraction (XRD), differential scanning calorimetry (DSC), scanning electron microscopy (SEM) and thermogravimetric analysis (TGA).

EVA, containing 18% vinyl acetate with MFI of 1.85 g/10 min at 190 C and density of 0.94 g/cm3, was purchased from Hyundai Petrochemical Co., Korea. The organoclay used in this study was a dimethyl ditallow ammonium montmorillonite (Cloisite 15A), Southern Clay Products, Canada. PE-graft-maleic anhydride copolymer, as a compatibilizer with density of 0.92 g/cm3, was supplied by Kimia Javid Sepahan Co., Iran. Also, Irganox 1010 (tris-(2,4-di tert-butylphenyl)-phosphate), as a stabilizer with density of 1.15 g/cm3, was purchase from Ciba Co., Switzerland. 2.2. Experimental design The common approach in the research plan is to change one parameter at a time which involves numerous experimental runs to fully explore the inuence of the entire parameter on the output results. However, the DOE approach such as Taguchi method can be utilized as a powerful analysis tool to minimize the number of experiments while retaining quality of data collection [17]. In addition, the analysis of variance (ANOVA) on the collected data from the Taguchis DOE can be used to optimize the performance characteristic [18]. According to the objectives of the present study, three factors were introduced as affecting the mechanical properties of HDPE/ EVA/organoclay nanocomposite which were the organoclay, compatibilizer and stabilizer loadings. Each of these factors considered to be varying at four levels that are summarized in Table 1. Consequently, from the number of factors and levels that have been selected, the orthogonal array of L16 type was used as shown in Table 2. 2.3. Sample preparation Nanocomposite samples were prepared by melt blending in an internal mixer (Plasticorder PL2000, Brabender). The HDPE was rst mixed in the internal mixer at 190 C, 60 rpm for 5 min and then pre-weighed amounts of the EVA, organoclay, compatibilizer and stabilizer were added to the mixer and the mixing process continued for a further 10 min under the same conditions. Each of the molten samples was compression molded into sheets with a thickness of about 2 mm using a hydraulic press at 190 C and 150 bar for 3 min. The material was subsequently cooled under pressure to 30 C, which took approximately 10 min. All the samples were immediately sealed in plastic bags and stored in a vacuum desiccator for at least 72 h prior to experiments. Table 2 presents the formulation and designation of the samples. It should be pointed out that all the formulations included a matrix of 70 wt% PE and 30 wt% EVA. These ratios were the typical values found in the literature for PE/EVA blends preparations [19,20]. 2.4. Characterization methods 2.4.1. Tensile properties Tensile properties were measured according to ASTM D638 [21] for the prepared specimens using a servohydraulic testing machine (Santam-SPM20), at a cross-head speed of 50 mm/min. EM was

2. Experimental 2.1. Material The HDPE, with density of 0.95 g/cm3 and melt ow index (MFI) of 0.35 g/10 min at 190 C, was supplied by Bandar Imam Petrochemical Company of Iran (Poliran HB0035). The weight-average molecular weight and PDI were obtained by gel permeation chromatography (GPC) as 225,000 g/mol and 20.5, respectively [16].

Table 1 Selected factors and their respective levels. Control factor Level 1 Organoclay (Phra) Compatibilizer (Phr) Stabilizer (Phr)
a

2 1 2 1

3 3 6 2

4 5 9 3

0 0 0

Phr: Parts per hundred resins of (70 wt% HDPE and 30 wt% EVA).

S. Akhlaghi et al. / Materials and Design 33 (2012) 273283 Table 2 The L16 orthogonal array for selected factors and levels and the corresponding mechanical response for each trial. Sample no. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 Organoclay (Phr) 0 0 0 0 1 1 1 1 3 3 3 3 5 5 5 5 Compatibilizer (Phr) 0 2 6 9 0 2 6 9 0 2 6 9 0 2 6 9 Stabilizer (Phr) 0 1 2 3 1 0 3 2 2 3 0 1 3 2 1 0 EM (%) (MPa) 21.5 0.17 27 0.24 29.5 0.52 27.4 0.19 25 0.32 25.5 0.35 30 0.61 27 0.2 26.8 0.14 31.8 0.42 26 0.21 27.4 0.33 22 0.4 26.2 0.39 28 0.25 25 0.18 TS (%) (MPa) 999 2.16 980 3.51 971 1.18 960 2.2 1080 2.41 1065 3.58 1050 2.08 990 3.56 1185 2.52 1200 4 1060 3.24 1084 2.22 1130 3.65 1092 2.47 1074 3.69 986 2.94 EB (%) 221 1.01 391 0.85 460 1.48 480 1.17 242 2.09 397 1.1 450 2.59 480 2.03 305 0.96 543 2.1 521 2.55 486 1.64 225 0.92 377 1.18 318 2.09 450 1.12

275

calculated from the slope of the low strain region of the tensile curve. Average values from ve experiments were determined. 2.4.2. XRD A Philips PW1840 X-ray Diffractometer with Cu Ka radiation (k = 0.154 nm) at a generator voltage of 40 kV and a current of 30 mA was used. The data were collected between 1 and 30 at ambient temperature with a scanning speed of 0.02 deg/s and step size of 0.02. 2.4.3. DSC DSC (Polymer Laboratories, PL-DSC) was used to study the crystallization behavior of the samples under nitrogen atmosphere. Indium and tin were used for the calibration of heat of fusion and melting temperature. The samples were rst heated at 190 C for 5 min and then standard scans were performed by cooling them down to 20 C at 10 C/min and nally heating from 20 C to 190 C at 10 C/min. Crystallization Enthalpies for the HDPE-rich and EVA-rich phases were calculated from the DSC traces using the enthalpies of fusion of the perfectly crystalline polyethylene (298 J/g [22]) and EVA (68 J/g [23]), respectively. 2.4.4. SEM SEM (Tescan VEGA II) images were used to study the phase morphology of the samples. The samples were cryogenically fractured in liquid nitrogen and the fractured surfaces were etched by hot-xylene for 6 h, which preferentially etched out the EVA phase. Then the samples were sputter-coated with a thin layer of gold. Also, the extent of dispersion of the polymeric components in the nanocomposites was evaluated based on the SEM micrographs. The micrographs of selected samples were examined using ImageJ analysis and the average particle diameter (Dn) was calculated. 2.4.5. TGA Thermogravimetric analysis of the samples was carried out using a Polymer Laboratories TGA-PL apparatus in the temperature range 25600 C in a nitrogen atmosphere at a heating rate of 10 C/min. 3. Results and discussion 3.1. DOE analysis of mechanical properties The results obtained regarding EM, TS and EB of all the prepared samples are listed in Table 2. In order to investigate the role of the

selected factors on the samples EM, TS and EB, the main effect of each factor must be taken into account. The mean effect (F) of a dened factor at each of the levels (Ln; n represents the levels number = 1, 2, 3 and 4) is obtained by adding the results of all trials P conditions ( yi) at the level considered and then dividing by the number of data points added (N) [17]:

F Ln

Xy

Figs. 13 show the main effects of the compatibilizer, organoclay and stabilizer contents on the mechanical properties of the HDPE/EVA nanocomposites with a 95% condence level. As it can

Fig. 1. Mean effect of the compatibilizer on the EM, TS and EB of the HDPE/EVA systems.

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Fig. 2. Mean effect of the organoclay on the EM, TS and EB of the HDPE/EVA systems.

Fig. 3. Mean effect of the stabilizer on the EM, TS and EB of the HDPE/EVA systems.

be seen from Fig. 1, although TS and EB increased with the addition of the compatibilizer, EM decreased as the compatibilizer content was increased. The increase of the ultimate properties in the compatibilized samples can be interpreted by the formation of copolymer at the interface between the two polymers, which acts as a coupling agent for the PE and EVA chains [24]. Whereas, the decrease of EM can be attributed to the fact that compatibilizer itself has lower EM [25]. In the other words, these observations pointed to the softening effect of the compatibilizer on the prepared samples [26]. Moreover, it is obvious from Fig. 2 that increasing of the organoclay loading to 3 phr resulted in an improvement about 15.42% in the EM of the prepared nanocomposites. Indeed, the organoclay had a much higher EM than the polymeric matrix [27] and thus the EM enhancement by the inclusion of the Cloisite 15A could be easily understood based on the mixtures rule. On the contrary, there is a reduction with TS and EB upon the increase of the organoclay content. This phenomenon has been already observed by other authors and on the majority of cases has been explained with hardening effect of organoclay [28] and poor interfacial interactions between nanoparticles and polymeric matrix [29]. As depicted in Fig. 3, the stabilizer alone has no clear effect on the mechanical properties of the prepared samples. In order to nd out the statistical signicance of the organoclay, compatibilizer and stabilizer and also their optimum concentrations, leading to the optimized mechanical properties of the prepared nanocomposites, ANOVA was performed on the experimental data. The standard analysis based ANOVA began with calculation of the total value of responses (T) calculated from [17]:

m X r X i 1 j 1

yij

where m is the total number of trials = 16 and r is the total number of repetitions = 5. Thereafter, the correction factor (CF) was determined from [17]:

CF

r2 N

where N is the total number of experiments = 16 5 = 80. The total sum of square deviations (SST) was then calculated from the following equation [18]:

SST

m X r X i1 j 1

y2 ij CF

Furthermore, the sum of squares due to a factor (SS) was obtained through [18]:

" SS

F2 L1

NF L1

F2 L2 NF L2

F2 L3 NF L3

F2 L4 NF L4

# CF 5

where N F L1 , NF L2 , N F L3 and N F L4 are the number of trails with factor F at 1, 2, 3 and 4 levels, respectively. SS can be calculated for each of the factors; i.e. SS1, SS2 and SS3 which are related to the sum of squares due to organoclay, compatibilizer and stabilizer content, respectively. Error sum of squares can be represented by the following equation [18]:

SSe SST SS1 SS2 SS3

S. Akhlaghi et al. / Materials and Design 33 (2012) 273283 Table 3 ANOVA results for percent of contributions of entire factors and the optimization of mechanical properties in various cases. Optimization basis Percent of contribution Organoclay (%) EM TS EB EM and TS EM and EB TS and EB EM and TS and EB 54 48 45 56 51 41 52 Compatibilizer (%) 13 31 33 16 25 35 22 Stabilizer (%) 33 21 22 28 24 24 26 Optimized formulation Organoclay (Phr) 3 3 3 3 3 3 3 Compatibilizer (Phr) 2 6 9 2 2 6 2 Stabilizer (Phr) 3 3 3 3 3 3 3

277

the symbol e stands for error term. Eventually, the percentage contribution (P) of each factor was given by [18]:

SS0 100 SST

where

SS0 SS V e 3

and Ve is error variance, equals to SSe/3, here. The values of the percentage contribution were determined based on the above mentioned procedure and the results are presented in Table 3. In addition, the optimum levels of each factor for various optimization bases were also listed in Table 3. The most interesting point regarding the ANOVA calculations is the fact that all the optimized formulations contained 3 phr of the stabilizer in addition to certain amount of the organoclay and compatibilizer. Also, the stabilizer content contributes to 2133% of all the optimization bases. It is obvious that the optimized formulation with the highest EM, EB and TS, simultaneously contained 3 phr of the organoclay, 2 phr of the compatibilizer and 3 phr of the stabilizer. Although, the effect of the organoclay and compatibilizer on the mechanical properties of nanocomposites have been the subjects of many research works in recent years, the role of stabilizer in this regard has been remained to be elucidated in details. To shed more light on this issue, a possible hypothesis put forward based on the fact that the alkylammonium molecules of the organic modier of the Cloisite 15A could be degraded to some extent when exposed to shear stress at high temperature during the samples melt processing [3032]. The degradation reaction products then may negatively inuence the overall mechanical behavior of the samples [25]. Accordingly, the stabilizer could play a role in prevention of the organic modier to undergo such degradation reactions. Actually, the thermal degradation generally proceeds either by Hofmann elimination (Scheme 1a) and/or an SN2 nucleophilic

substitution reaction (Scheme 1b) [31]. In the former reaction path, b-carbon of the alkyl group loses a hydrogen atom, yielding a-olens and a free amine; thereafter, the transformation of the a-olens into carbonyl containing compounds like peroxyacids, esters, lactones as well as aldehydes and carboxylic acids takes place in the presence of oxygen and water (Scheme 1a) [31]. On the other hand, the occurrence of the later which is more probable for the present case due to the nature of the organic modier of Cloisite 15A [30], leads to Nucleophilic attack of the chloride onto R4N+, yielding tertiary amines, chloroalkanes and alkenes (Scheme 1b) [30]. Consequently, as reported very recently by some authors, the aforementioned degradation products with high afnities to the PE matrix can diffuse quickly from the organoclay galleries toward the polymeric phase, leading to the collapse of the nanoclay tactoids following by the deterioration of the mechanical properties [25,33]. The properties deterioration phenomenon would be prohibited by the stabilizer which prevents the interactions between the a-olen and oxygen. Furthermore, it is believed that the carboxyl groups produced from the degradation of the organic modier can also react with the anhydride groups of the PE-graft-maleic anhydride compatibilizer and deactivate its compatibilizing role [25]. Therefore, IRGANOX 1010 stabilizer could also contribute to the increased efciency of the compatibilizer in the present nanocomposites. Regarding the determining role of the stabilizer on the efciency of the organoclay, a parameter introduced as the stabilizer/organoclay (S/OC) weight ratio for further investigations.

3.2. d-spacing and lateral crystal size measurements (XRD) Since the mechanical properties are directly related to the intercalation/exfoliation degree of the clay nanoparticle, XRD experiments were performed on the selected samples, Fig. 4. The selected samples were the neat HDPE/EVA as well as samples 6,

Scheme 1. Thermal degradation paths of the organic modier of the Cloisite 15A: (a) Hofmann elimination and (b) SN2 nucleophilic substitution reaction.

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pristine organoclay powder and the selected samples. As it can be observed, the formation of prevalent intercalated morphology is evident from the shifts of the basal peak of pristine organoclay towards lower diffraction angles in the organoclay containing samples. The extent of intercalation appears to be dependent on the samples S/OC values as implied from the samples d001 increasing with their S/OC ratios. It is interesting to note that sample 10 which showed the optimized mechanical properties, had the largest d001 value. This nding suggests that a sufcient amount of the stabilizer is required to achieve high levels of intercalation. Actually, by decomposition of the organic modier of the organoclay, the silicate layers become hydrophilic as they were before organic treatment [35]. This can markedly reduce the polymerorganoclay interaction probability. Therefore, small amounts of polymer chains could diffuse into the galleries of the organoclay, leading to the lower interlayer spacings [35]. On the other hand, the protective effect of the stabilizer on the organic modier led to the higher miscibility between the organoclay and polymeric matrix which favored the penetration of the polymeric chains between the silicate layers. Furthermore, the XRD patterns showed two diffraction peaks in 2h range of 2124, corresponding to the (1 1 0) and (2 0 0) lattice planes of the HDPE and PE fractions of the EVA [23]. Considering the peaks width at half height (b) and diffraction angles (2h) of these crystal planes, one can calculate the lateral crystal size (L) using the Scherrers equation [33]:

Kk b cos h

10

Fig. 4. XRD patterns of Cloisite 15A and sample 1 (S/OC = 0 phr, compatibilizer = 0 phr), sample 6 (S/OC = 0 phr, compatibilizer = 2 phr), sample 9 (S/OC = 2/3 phr, compatibilizer = 0 phr), sample 10 (S/OC = 1 phr, compatibilizer = 2 phr), sample 12 (S/OC = 1/3 phr, compatibilizer = 9 phr) and sample 15 (S/OC = 1/5 phr, compatibilizer = 6 phr).

where K is a structural factor, usually taken as 0.92 for PE [23]. The calculated values for crystal domain sizes of the organoclay containing samples are lower than the pure HDPE/EVA blend (Table 4). Also, the overall degrees of crystalinity (Xco) of the selected samples were determined from the integral intensities of the amorphous (Acr) and crystalline (Aam) contributions of the XRD patterns, based on Herman and Weidinger [33]:

X co

Acr Acr 2:17Aam

11

9, 10, 12 and 15 of Table 2 with the S/OC ratios between 0 and 1 (Table 4). It is well known that the positions of diffraction peaks on the XRD patterns of nanocomposites between 2h = 010 provides some information concerning the interlayer spacing (d) of the silicate layers of the organoclay through the Braggs equation [34]:

k 2 sin h

where 2h is diffraction angle and k = 1.514 is the wavelength of the incident radiation. Table 4 presents the characteristic 2h and the corresponding basal spacing determined from Eq. (9) for the

It should be noted that the samples crystalinities were decreased with the addition of the organoclay, as well (Table 4). Considering the fact that the spherulite growth stage is impressively hindered by the dispersed organoclay platelets, the reduction in the bulk crystallization rate and crystal domain sizes may be resulted in lower degree of crystallinity [36]. Another interesting nding is the fact that the reduction of L and Xc is more pronounced for the samples with higher S/OC values. This, we believe, is attributed to the higher miscibility between the nanoclay organic modier and crystallizable polymeric matrix in the samples with higher S/OC values which could lead to lower surface energy difference between the organoclay and pure polymer, imposing more disturbances upon the crystallization process [37]. 3.3. Crystallization and melting behavior (DSC) In order to obtain better understanding of the crystallization and melting behaviors, DSC experiments were also performed on the selected samples. Figs. 5 and 6 represent the DSC melting and crystallization traces of the neat HDPE/EVA system (sample 1) along with its selected nanocomposites. Two peaks are observed in the thermograms of each sample. The low and high temperature peaks of Figs. 5 and 6 are ascribed to the EVA-rich and HDPE-rich phases of the samples, respectively [23]. Melting and crystallization temperatures (Tm and Tc) and enthalpies (DHm and DHc) of both phases were determined form the DSC curves and listed in

Table 4 Diffraction angle and corresponding interlayer spacing of Cloisite 15A and selected samples, together with lateral crystal size and overall crystalinity of pure HDPE/EVA and its nanocomposites, obtained from XRD. Sample S/OC Organoclay 2h () Cloisite 15A Sample 1 Sample 6 Sample 9 Sample 10 Sample 12 Sample 15 0 2/3 1 1/3 1/5 2.80 2.00 1.85 1.81 1.93 1.95 d001 (nm) 3.48 4.41 4.76 4.89 4.57 4.51 HDPE/EVA L110 (nm) 22.72 21.05 20 19.98 20.68 20.72 L200 (nm) 21.39 19.68 18.42 18.31 19.17 19.21 72.26 64.94 61.05 60.94 61.49 62.28 Xoc (%)

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Fig. 5. DSC melting curves of pure HDPE/EVA system and sample 1 (S/OC = 0 phr, compatibilizer = 0 phr), sample 6 (S/OC = 0 phr, compatibilizer = 2 phr), sample 9 (S/OC = 2/3 phr, compatibilizer = 0 phr), sample 10 (S/OC = 1 phr, compatibilizer = 2 phr), sample 12 (S/OC = 1/3 phr, compatibilizer = 9 phr) and sample 15 (S/OC = 1/5 phr, compatibilizer = 6 phr).

Fig. 6. DSC crystallization curves of pure HDPE/EVA system and sample 1 (S/ OC = 0 phr, compatibilizer = 0 phr), sample 6 (S/OC = 0 phr, compatibilizer = 2 phr), sample 9 (S/OC = 2/3 phr, compatibilizer = 0 phr), sample 10 (S/OC = 1 phr, compatibilizer = 2 phr), sample 12 (S/OC = 1/3 phr, compatibilizer = 9 phr) and sample 15 (S/OC = 1/5 phr, compatibilizer = 6 phr).

Table 5. It is seen that Tm, Tc, DHm and DHc of the HDPE-rich regions of the nanocomposites are lower than those of the neat HDPE/EVA blend (sample 1). Although Tm, DHm and DHc depression by the addition of nanoparticle is a common report of various research works, most of the researches believe that because of the nucleation effects, Tcs of the nanocomposites would be higher than their corresponding neat blends [35,37,38]. However, the nanoparticles did not play a role as a nucleating agent in the present nanocomposites. This in agreement with other reports where the nucleation efciencies of the organoclay dramatically decreases in the systems containing high molecular weight PE (here, Mw = 250,000 g/ mol) [39]. The decrement of the HDPE-rich phase melting point in the nanocomposites can be discussed in terms of the systems viscosities. It seems that the adsorption of polymer chains on the organoclay surfaces increased the viscosity of the nanocomposites which in turn negatively affected the crystallization growth stage [38]. Thus, the more defective crystals in the nanocomposites would have lower Tms as it was also shown earlier based on the XRD investigations. The above mentioned increase in the viscosity can be corroborated with the investigation of torque vs. time curves

provided by the internal mixer equipment software during the melt processing of the samples. It is established that the steadystate or stabilized torque (TOstab) is approximately equivalent to viscosity of the compound [40]. In addition, the specic energy (Espec) spent during mixing procedure can also be used to rank qualitatively the viscosity level of the samples through the following equation [22]:

Espec

2G w

M dt

12

where G, M and w are rotor speed, torque and weight of the sample, R respectively. Also the integral, M dt, indicating the totalized torque, is the measured area under the torque vs. time curve. As it can be inferred from Table 5, TOstab and Espec were increased by both the organoclay content and the S/OC ratio. Nevertheless, there are no notable changes in the melting or crystallization temperatures and enthalpies of the EVA phase with either addition of the organoclay or the S/OC ratio. Also, as shown in Table 5, a decrease of 6.61% in the crystalinity of the HDPE-rich phase (XcHDPE) occurred for the sample with the highest S/OC (sample 10) compared to the neat HDPE/EVA blend (sample 1),

Table 5 Melting and crystallization characteristics of HDPE and EVA-rich phases of neat HDPE/EVA blend and its nanocomposites along with samples TOstab and Espec. Sample no. HDPE phase Tm (C) 1 6 9 10 12 15 140.45 137.61 134.21 132.84 135.81 136.41 Tc (C) 113.42 110.04 107.45 106.02 109.24 108.90 EVA phase TOstab (N m) Tc (C) 66.64 66.61 66.21 66.48 66.27 66.29 Espec (J/g)

DHm (J/g)
119.14 115.56 111.97 111.26 113.49 114.02

DHc (J/g)
130.25 126.37 115.45 110.58 122.22 122.81

XcHDPE (%) 58.09 56.34 54.59 54.25 55.33 55.60

Tm (C) 88.48 88.14 88.21 88.19 88.51 88.29

DHm (J/g)
3.88 3.61 3.59 3.64 3.47 3.51

DHc (J/g)
5.41 5.35 5.48 5.37 4.87 5.29

XcEVA (%) 19.08 17.76 17.66 17.17 17.07 17.26 12.85 14.25 16.45 17.40 15.35 14.90 651.32 710.56 852.69 880.07 804.91 763.33

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Fig. 7. SEM micrographs of pure HDPE/EVA system and sample 1 (S/OC = 0 phr, compatibilizer = 0 phr), sample 6 (S/OC = 0 phr, compatibilizer = 2 phr), sample 9 (S/OC = 2/ 3 phr, compatibilizer = 0 phr), sample 10 (S/OC = 1 phr, compatibilizer = 2 phr), sample 12 (S/OC = 1/3 phr, compatibilizer = 9 phr) and sample 15 (S/OC = 1/5 phr, compatibilizer = 6 phr).

whereas no considerable change observed for the crystalinity of the EVA-rich phase (XcEVA) of the studied samples. Therefore, it can be inferred that the organoclay mostly resided in the HDPErich phase due to the fact that it merely affected the HDPE-rich regions characteristics. As it was explained in the experimental section, the HDPE component had already been melted as the organoclay was added to the mixing chamber in our mixing procedure. Therefore, the organoclay concentrated preferably in the

HDPE-rich regions although the EVA phase was thermodynamically more favorable in this regard [41]. However, since the organoclay did not have signicant impact on the EVA phase properties, the organoclay migration from the HDPE to the EVA phase seems not happened. This may be ascribed to the high viscosity of the HDPE phase which impeded the transfer of the organoclay to the EVA phase. Furthermore, one cannot ignore the impressive contribution of the stabilizer and compatibilizer agents to provide

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Table 6 Tonest,1, Tmax,1, Tonest,2 and Tmax,2 of neat HDPE/EVA system and its selected nanocomposites. Sample no. 1 6 9 10 12 15 Tonest,1 (C) 338.16 340.59 343.12 343.95 342.42 342.02 Tmax,1 (C) 342.12 348.01 355.48 357.90 355.26 352.65 Tonest,2 (C) 401.18 403.64 407.87 409.18 406.01 404.44 Tmax,2 (C) 487.91 490.47 494.56 497.72 492.72 491.53

Fig. 8. DTG curves of pure HDPE/EVA system and sample 1 (S/OC = 0 phr, compatibilizer = 0 phr), sample 6 (S/OC = 0 phr, compatibilizer = 2 phr), sample 9 (S/OC = 2/3 phr, compatibilizer = 0 phr), sample 10 (S/OC = 1 phr, compatibilizer = 2 phr), sample 12 (S/OC = 1/3 phr, compatibilizer = 9 phr) and sample 15 (S/OC = 1/5 phr, compatibilizer = 6 phr).

of the HDPE against the EVA as well as the composition of the phases, the HDPE component is the matrix phase. The observed rough interface between the HDPE and EVA in sample 1 pointed to incompatibility of these two polymers. However, according to the calculated Dns of the dispersed phase it is clear that the EVA domain sizes decreased notably in the presence of the organoclay. Such a domain size reduction can be attributed to the compatibilizing effect of the organoclay in the prepared nanocomposites which is already reported by other authors [4144]. The most interesting point regarding the SEM results was the intensication of the EVA drop size reduction with the increase of the S/OC ratio in most of the samples. Particularly, sample 10 which was the best one regarding the mechanical properties, possessed the smallest Dn value. This nding seems to be related to the high matrix viscosity and homogeneous dispersion of the organoclay in this sample, as it was discussed earlier in this work. However, despite the higher S/OC value of sample 9 (=2/3) against sample 12 (=1/3), there is an exception to the expected trend and the average EVA drop size of the former was larger than that of the later. A second look to the formulations of the aforementioned samples (Table 2) reveals that sample 12 contained 9 phr of the compatibilizer while sample 9 was compatibilizer free. Actually, the PE-graft-maleic anhydride copolymers as a compatibilizer for the HDPE/EVA system, decreased the interfacial tension between the major and minor phases, providing ner dispersion of the minor phase in the matrix [43,19]. Therefore, it can be concluded that the organoclay could have its maximum compatibilizing effect, only in the presence of the PE-graft-maleic anhydride compatibilizer. 3.5. Thermal degradation assessment (TGA) Eventually, thermal stabilities of the selected HDPE/EVA systems were discussed in terms of their DTG and TGA curves (Figs. 8 and 9). As shown in Fig. 8, all the samples display a two-step thermal degradation process. The rst stage occurring between 350 and 400 C is related to the deacylation of the EVA phase through radical and ionic b-elimination mechanisms [13]. In addition, the second step (400450 C) involves the degradation of the HDPE phase accompanied with the decomposition of the polyacetyleneethylene chains formed in the rst stage [13]. The rst degradation onset temperature (Tonst,1) and the rst maximum weight loss temperature (Tmax,1) as well as the second ones (Tonst,2 and Tmax,2) were determined from the DTG and TGA curves and listed in Table 6. It can be seen that all the thermal degradation temperatures of the nanocomposites are higher than those of the neat blend. Tonst,1 and Tmax,1 increasing with the organoclay addition, however, is inconsistent with other investigations in which the organoclay was found to accelerate the deacylation of EVA copolymer due to the catalytic activity of the acidic sites, inherently existing in the nanoclay structure [1113]. This nding can also be regarded as another evidence, lending credence to the hypothesis that the organoclay particles were localized preferentially within the HDPE-rich phase. Nevertheless, the acidic sites of the

Fig. 9. TGA curves of pure HDPE/EVA system and sample 1 (S/OC = 0 phr, compatibilizer = 0 phr), sample 6 (S/OC = 0 phr, compatibilizer = 2 phr), sample 9 (S/OC = 2/3 phr, compatibilizer = 0 phr), sample 10 (S/OC = 1 phr, compatibilizer = 2 phr), sample 12 (S/OC = 1/3 phr, compatibilizer = 9 phr) and sample 15 (S/OC = 1/5 phr, compatibilizer = 6 phr).

favorable HDPEorganoclay interactions. In this view, the stabilization mechanism ensured the miscibility of the organic modier with the HDPE chains and the compatibilization process offered specic interactions between the major phase and the organoclay hydroxyl groups. 3.4. Direct observation of morphology (SEM) Fig. 7 represents the SEM micrographs of the selected specimens. The holes displayed in the SEM images represent the EVA domains that had been etched out by hot xylene. The average EVA domain size (Dn) for each sample has been shown on its SEM micrograph. In all the samples, due to relative high viscosity

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organoclay have shown to be sufciently active to abstract single electrons from donor molecules of the PE phase [44]. This would result in the formation of free radicals on the PE chains which are highly capable of further accelerating the thermal oxidation of HDPE-rich regions in the second step of thermal degradation. Of importance, however, is the role of the stabilizer to deactivate the acidic sites of the organoclay, making it chemically inert in respect to the thermal oxidation of the PE [45]. Besides, the improvement in thermal stability may be addressed to the barrier effect of the organoclay [46]. It is believed that the intercalated organoclay platelets disturb the diffusion of oxygen molecules needed for initiating the oxidative degradation, by creating a tortuous path in the matrix [14]. In addition, this barrier effect may also slow down the rate of mass loss by hindering the escape of the volatile products of the thermal degradation process from the nanocomposites [46]. Interestingly, regarding the data reported in Table 6, it is clear that the samples degradation temperatures increased with their S/OC values. Therefore, Irganox 1010 not only contributed to the samples thermal stability enhancing as a common heat stabilizer, but also by affecting the dispersed phase domain size. In other words, improving the thermal stability is more impressive when one uses appropriate amount of stabilizer in combination with organoclay.

4. Conclusion The inuences of the organoclay, compatibilizer and stabilizer contents on the mechanical properties of the HDPE/EVA nanocomposites were statistically analyzed using Taguchi method. The most interesting nding regarding the data obtained by ANOVA was the fact that all the optimized formulations contained 3 phr of the stabilizer in addition to certain amounts of the organoclay and compatibilizer. Concerning the fact that the organic modier of the nanoclay could be degraded during the samples preparation process, one can suggest that the stabilizer prevented or at least reduced the thermo-oxidative degradation of the organoclay modier, thereby leading to the better mechanical properties. In addition, the XRD and SEM results showed that the morphological properties of the nanocomposites are strongly affected by their S/ OC ratio. Furthermore, the organoclay appeared to be mostly resided in the HDPE-rich phase due to the fact that it merely affected the HDPE-rich regions characteristics. Finally, based on the TGA results, the improvement of thermal stability resulted from the incorporation of the organoclay in the blend sample was more pronounced for the nanocomposites with higher S/OC value.

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